Doped perovskite having improved stability, and solar cells made thereof

ABSTRACT

A light-harvesting material comprises a perovskite absorber doped with a metal chalcogenide. The light-harvesting material may be used in a photovoltaic device, comprising (1) a first conductive layer, (2) an optional blocking layer, on the first conductive layer, (3) a semiconductor layer, on the first conductive layer, (4) a light-harvesting material, on the semiconductor layer, (5) a hole transport material, on the light-harvesting material, and (6) a second conductive layer, on the hole transport material.

FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with government support under CBET-1150617 awarded by the National Science Foundation. The government has certain rights in the invention.

BACKGROUND

Photovoltaic (PV) systems are systems that convert light into electricity. All photovoltaic systems share a few common parts. All photovoltaic systems include light-harvesting function, a charge-separating function, charge-transporting function, and a charge collecting function.

In the past several years, organic-inorganic metal halide perovskites (ABX₃, A=CH₃NH₃ ⁺, (NH₂)₂CH⁺, B=Pb²⁺, Sn²⁺, X=Cl⁻, Br⁻, I⁻) have risen to be a class of promising new photovoltaic materials due to their attractive merits, such as solution processability, low cost of material precursors and ease of device fabrication.¹⁻³ Among the class of hybrid perovskites, methylammonium lead iodide (CH₃NH₃PbI₃) represents an outstanding light absorber (1.5×10⁴/cm at 550 nm)^(4,5) with superior photovoltaic properties such as ease of free carrier generations⁶, long carrier diffusion lengths^(7,8) even with its moderate mobilities,⁹ and the surprisingly long carrier lifetimes^(7,10), and has attracted extensive attention for its phenomenal photovoltaic performance, as well as other emerging properties including ferroelectrics and nano-lasing.¹¹⁻²³ Although CH₃NH₃PbI₃ owns such prominences, it suffers from several inherent problems, including lead toxicity, current-voltage hysteresis, and low stability in humidity.²⁴⁻²⁷ According to perovskite crystal structures and previous studies, the first step of structural degradation due to moisture involves the formation of hydrated PbX₆ ⁴⁻ intermediate and removal of the methylammonium from the sub-lattice structure, this produces a large amount of charge imbalance and the resultant self-repelling PbI₃ ⁻ lattice collapses to generate PbI₂. In order to tackle this problem, modifications of chemical composition in the perovskite active layer have been practiced by introducing dopants and new chemical moieties geared towards moisture tolerance.^(4,28,29) Successful examples of enhancing moisture stability of perovskites was previously realized through partially replacing the halides with pseudohalides such as SCN⁻ or partially replacing the CH₃NH₃ ⁺ with butylammonium, so as to convert the three-dimensional perovskite structure to a Ruddlesden-Popper type, two-dimensional perovskite structures.^(4,30-33) However, the resulting layered structure hinders charge transport through structurally confining photocarriers in 2-D inorganic sheets of the materials.^(33, 34) Thus, it is imperative to explore chemical pathways that retain the 3-dimensionality of the perovskite structure and good photo-absorption while still enhancing the chemical stability of the entire structure to battle the invasion of water molecules.

SUMMARY

In a first aspect, the present invention is a light-harvesting material, comprising a perovskite absorber doped with a metal chalcogenide.

In a second aspect, the light-harvesting material comprises a perovskite absorber. The perovskite absorber has the formula ABX₃, A is selected from the group consisting of alkyl ammonium, formamidinium and mixtures thereof, B is selected from the group consisting of lead, tin and mixtures thereof, X is selected from the group consisting of F, Cl, Br, SCN, I and mixtures thereof, the metal of the metal chalcogenide is selected from the group consisting lead, tin and mixtures thereof, and the chalcogenide of the metal chalcogenide is selected from the group consisting S, Se, Te and mixtures thereof. Preferably A comprises methyl ammonium, B comprises lead, X comprises I, and the chalcogenide comprises Se.

In a third aspect the present invention is a photovoltaic device, comprising (1) a first conductive layer, (2) an optional electron blocking layer, on the first conductive layer, (3) a semiconductor layer, on the optional electron blocking layer, (4) a light-harvesting material, on the semiconductor layer, (5) a hole transport material, on the light-harvesting material, and (6) a second conductive layer, on the hole transport material. The light-harvesting material comprises a perovskite absorber doped with a metal chalcogenide.

In a fourth aspect, the present invention is a method of making a perovskite absorber, comprising forming a solution comprising: a first component selected from the group consisting of alkyl ammonium, formamidinium and mixtures thereof, a second component selected from the group consisting of lead, tin, and mixtures thereof, a third component selected from the group consisting of F, Cl, Br, SCN, I and mixtures thereof, and a fourth component selected from S, Se, Te or mixtures thereof, and forming the perovskite absorber from the solution. The perovskite absorber is doped with a metal chalcogenide.

DEFINITIONS

A “perovskite solar cell” or “perovskite-type solar cell” is a solar cell which includes a perovskite absorber as the light-harvesting element.

A “perovskite absorber” is a compound of formula ABX₃, where A is a metal atom such as lead or tin, B is a counter ion (typically an alkyl ammonium compound), and X is a halide (F, Cl, Br, or I) or pseudohalide (such as SCN), which forms crystals of the perovskite structure. Examples include CH₃NH₃PbX₃ (3-dimensional perovskite) and H₂NCHNH₂PbX₃ (3-dimensional perovskite) and CH₃NH₃Pb(SCN)₂I (Ruddlesden-Popper type). Examples of structure which are perovskite structures included 3-dimensional perovskite, Ruddlesden-Popper type and Dion-Jacobson type. In some cases, the perovskite absorber is doped, which may result in additional atoms located in interstitial sites and/or the formation of vacancies. Examples of a perovskite absorber that is doped included CH₃NH₃PbI₃:10% PbSe, which is CH₃NH₃PbI₃ doped with 10% PbSe, and therefore the stoichiometry may deviate from the ABX₃ formula.

All percentages are weight/weight (w/w) percentages, unless indicated otherwise.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a schematic depiction of the hypothesized PbSe doped CH₃NH₃PbI₃ lattice structure.

FIG. 2A shows a SEM image of surface morphology of 10% w/w PbSe doped CH₃NH₃PbI₃ thin film.

FIG. 2B shows an energy dispersive X-ray analysis of 10% w/w PbSe doped CH₃NH₃PbI₃ thin film.

FIG. 2C shows evolution of time-dependent reflectance spectra of pristine CH₃NH₃PbI₃ under 100% humidity at 40° C. under ambient illumination conditions.

FIG. 2D shows evolution of time-dependent reflectance spectra of 10% w/w PbSe doped CH₃NH₃PbI₃ thin films under 100% humidity at 40° C. under ambient illumination conditions.

FIG. 2E shows Kubelka-Munch plots of pristine CH₃NH₃PbI₃ thin films.

FIG. 2F shows Kubelka-Munch plots of 10% w/w PbSe doped CH₃NH₃PbI₃ thin films.

FIG. 2G shows powder X-ray diffraction spectra of pristine CH₃NH₃PbI₃ (bottom), 5% w/w PbSe doped CH₃NH₃PbI₃ (middle) and 10% w/w PbSe doped CH₃NH₃PbI₃ (top) samples, with crystallographic planes indicated above corresponding diffraction peaks of each trace to illustrate the shift of diffraction angles.

FIG. 2H shows infrared transmittance spectra of CH₃NH₃PbI₃ thin film (darker) and 10% w/w PbSe doped CH₃NH₃PbI₃ thin film (lighter).

FIG. 3A shows Photocurrent density-voltage (J-V) curves with forward (darker) and reverse (lighter) scans for 10% w/w PbSe doped CH₃NH₃PbI₃ champion cell.

FIG. 3B shows stable output of current density (darker) and power conversion efficiency (lighter) at maximum power with respect to time for the device.

FIG. 3C shows IPCE spectrum of 10% w/w PbSe doped CH₃NH₃PbI₃ based thin film with an integrated area current density of 16.35 mA/cm².

FIG. 4 is a stability graph showing water stability based on reflectance percent of 5% w/w doped CH₃NH₃PbI₃.

FIG. 5 shows fluorescence intensity of PbSe doped perovskite versus undoped perovskite.

FIG. 6A shows a stability plot of PbS doped CH₃NH₃PbI₃ in 100% humidity under ambient light, with photograph insets showing the change in the PbS doped material.

FIG. 6B is a graph of bandgap evolution over time of 10% w/w doped CH₃NH₃PbI₃.

FIG. 7 shows XRD spectra of 10% w/w PbS doped methyl ammonium lead iodide (top) and formamidinium lead iodide (bottom).

FIG. 8 shows a J-V plot of PbS doped formamidinium lead iodide (darker) and methyl ammonium lead iodide (lighter).

FIG. 9 shows a schematic diagram of a perovskite solar cell with listed components being preferred materials: a fluorinated tin oxide (FTO) anode covered with an electron blocking TiO₂ thin film, rutile TiO₂ nanowires, spin-coated CH₃NH₃PbI₃ layer, or spin-coated CH₃NH₃Pb(SCN)₂I layer and sprio-MeTAD layer, followed by a sputtered nickel cathode.

FIG. 10 shows the edges of silver electrodes which have reacted with iodides.

FIG. 11A shows a photograph of tested CH₃NH₃PbI₃ film at 0 minutes of aging time.

FIG. 11B shows a photograph of tested CH₃NH₃PbI₃ film at 30 minutes of aging time.

FIG. 12A shows a photograph of tested 10% w/w PbSe doped CH₃NH₃PbI₃ film at 0 minutes of aging time.

FIG. 12B shows a photograph of tested 10% w/w PbSe doped CH₃NH₃PbI₃ film at 60 minutes of aging time.

DETAILED DESCRIPTION

The present invention includes a light-harvesting material comprising a perovskite absorber and a dopant to increase the stability of the light-harvesting material to moisture. Preferably the perovskite absorber is an organic-inorganic metal halide (or pseudohalide) perovskite, and the dopant is a metal chalcogenide.

A “perovskite absorber” is a compound of formula ABX₃, where A is a metal atom such as lead or tin, B is a counter ion (typically an alkyl ammonium compound), and X is a halide (F, Cl, Br, or I) or pseudohalide (such as SCN, SeCN), which forms crystals of the perovskite structure. Examples include CH₃NH₃PbX₃ (3-dimensional perovskite) and H₂NCHNH₂PbX₃ (3-dimensional perovskite) and CH3NH3Pb(SCN)2I (Ruddlesden-Popper type). Examples of structure which are perovskite structures included 3-dimensional perovskite, Ruddlesden-Popper type and Dion-Jacobson type. In some cases, the perovskite absorber is doped, which may result in additional atoms located in interstitial sites and/or the formation of vacancies. Examples of a perovskite absorber that is doped included CH3NH3PbI3:10% PbSe, which is CH₃NH₃PbI₃ doped with 10% PbSe, and therefore the stoichiometry may deviate from the ABX₃ formula.

CH₃NH₃PbI₃ is known as an outstanding light absorber, but it is also known to have low stability in humidity. The present application demonstrates that by doping Se²⁻ in the form of PbSe into CH₃NH₃PbI₃ lattice, the moisture stability of perovskite remarkably, can be enhanced 200 fold, as signified by evolution of optical reflectance. Meanwhile, a phenomenal 10.4% power conversion efficiency was achieved.

The dopant may be present in an amount of 5 to 20% by weight of the light-harvesting material. At higher concentrations, it is possible that phase separation may begin to occur between the dopant and the perovskite absorber. Preferably the dopant is present in an amount of 7 to 12% by weight, most preferably 9 to 11% by weight.

The doped films of PbSe doped CH₃NH₃PbI₃ exhibited over two-hundred-fold improved stabilities as compared to conventional CH₃NH₃PbI₃ film, which degraded in half an hour in 100% humid environment. Powder diffraction and IR studies of 10% w/w PbSe doped CH₃NH₃PbI₃ confirms that an increase in the cubic nature of the perovskite lattice, with a decrease in tetragonal/octahedral nature, the presence of hydrogen-bonding like interactions, and the covalence of the perovskite lattice, which may contribute to the overall stability of organic-inorganic perovskite. The increase in the cubic nature appears to increase moisture resistance.

From the viewpoint of fundamental coordination chemistry, anions with a less electronegative nature (such as I⁻ vs Br⁻ and Cl⁻) are capable of forming chemical bonds with Pb²⁺ which are more covalent, thus favoring charge generation and hole transport.^(35,36) On the other hand, weak electronegativity in anions leads to weak attraction between the anionic framework and the organic cations, thus deteriorating the chemical stability. This is evident by the fact that doping Br⁻ helps the stability of the perovskite structure, but at the cost of greatly narrowed absorption in the visible spectrum (from 775 nm to 540 nm as upper limit).³⁷⁻³⁹

A higher order anionic charge should greatly increase such electrostatic interaction, in comparison to a monovalent halide, so as to stabilize CH₃NH₃ ⁺ from moisture solvation.⁴⁰ Such electron-rich environments of perovskite systems, induced by structural modifications, inspired a focus on multivalent ion doping—chalcogenides and pnictogenides such as S²⁻, Se²⁻ and N³⁻. With nitrogen being overly electronegative, compromises can thus be S²⁻ and Se²⁻. Synergistically, the ease of photoelectron transport⁴¹ and wide absorption spectra in lead chalcogenides is evident by the small bandgaps of lead(II) sulfide (PbS, 0.37 eV) and lead(II) selenide (PbSe, 0.28 eV) that are used as semiconductors.⁴²⁻⁴⁵ Indeed, the difference in electronegativity (Δ_(X)) between Pb and Se is even slightly smaller than that between Pb and I, (Δ_(X) for Pb—Se=0.68, Δ_(X) for Pb—I=0.79, on the Pauling Scale). As such, doping with PbSe would minimize any negative impact on the desired covalent nature of the inorganic framework in hybrid perovskite, while allowing for good charge transport.

The proposed crystal structure of 10% w/w PbSe doped CH₃NH₃PbI₃ takes into consideration that the periodically located Se²⁻ forms hydrogen-bond like interaction with CH₃NH₃ ⁺ in proximity, as illustrated in FIG. 1, confirming that the origin of moisture stability falls on the attracted CH₃NH₃ ⁺ groups through strong electrostatic interaction with Se²⁻. Moreover, the addition of Se²⁻ in the perovskite layer mitigates the chemical interaction between iodide and a silver counter electrode.

Doped perovskite absorbers can be used in a solar cell as a light-harvesting material, as illustrated in FIG. 9. The solar cell preferably includes a first conductive layer, 6; an optional electron blocking layer, 5, on the first conductive layer, a semiconductor layer, 4, on the optional electron blocking layer; a light-harvesting material, 3, on the semiconductor layer; a hole-transporting material, 2, on the light-harvesting layer; and a second conductive layer, 1, on the hole-transporting material.

Preferably, the first conductive layer is transparent, so that light may penetrate one side of the device and reach the light-harvesting material. Optionally, the first conductive layer may be on a substrate. Examples of substrates include glass, quartz and transparent polymeric materials, such as polycarbonate. Examples of transparent conductive layers include indium-tin oxide, fluorinated tin oxide, and aluminum-zinc oxide. Graphene may also be used as the first conductive layer. The first conductive layer may also be formed as a composite material and/or formed as multiple layers. For example, a planar substrate of glass may be coated with a layer of fluorinated tin oxide, and fine particles of fluorinated tin oxide applied to the surface and sintered together to provide the substrate and first conductive layer.

In an alternative configuration, such as that described in Patent Application Publication, Pub. No. US 2011/0220192, the first conductive layer, with the semiconductor layer and light harvesting material, are on the support, but spaced away from the electrode and second conducting layer, and not in direct electrical contact therewith. In operation of this alternative configuration, light does not need to travel through the first conductive layer, so a non-transparent conductive layer may be used, for example a metal such as nickel, gold, silver or platinum, or a conductive oxide, such as electrically conductive titanium suboxides.

The optional blocking layer, which serves to bind defective sites and suppress back electron transfer, and may have a different composition than the semiconductor layer, and is preferably a transparent insulating material, for example titanium dioxide (TiO₂), magnesium oxide (MgO), aluminum oxide (Al₂O₃), zirconium oxide (ZrO₂), boron nitride (BN), silicon oxide (SiO₂), diamond (C), barium titanate (BaTiO₃), and mixtures thereof. The blocking layer may also be formed of a transparent semiconductor material and preferably is an n-type semiconductor, for example titanium dioxide (TiO₂), zinc oxide (ZnO), zirconium oxide (ZrO₂), tungsten oxide (WO₃), molybdenum oxide (MoO₃), lead oxide (PbO), and mixtures thereof, or mixtures thereof with a transparent insulating material. It is important that the blocking layer be both conformal and compact.

The optional blocking layer preferably has a thickness of at most 20 nm, or may be present in an amount of at most 100 atomic layers. It may also be present as islands on the surface of the semiconductor layer, in which case the thickness may be expressed as an average thickness across the semiconductor layer, for example as less than one atomic layer.

The semiconductor layer, which is n-doped or n-type, may be a transparent semiconductor, such as titanium dioxide (TiO₂), zinc oxide (ZnO), zirconium oxide (ZrO₂), tungsten oxide (WO₃), molybdenum oxide (MoO₃), lead oxide (PbO) or mixtures thereof. Preferably, the semiconductor layer has a thickness of at most 100 nm, for example 1 to 100 nm, including 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 and 95 nm. If the semiconductor layer is not intrinsically formed as an n-type semiconductor, such as is the case with TiO₂, is may be chemically n-doped.

The semiconductor layer may be formed by physical vapor deposition, such as evaporation or sputtering, or by chemical deposition, such as atomic layer deposition, or by forming a thin layer of a precursor which is then decomposed to form the semiconductor layer. Electrochemical deposition or deposition from solution, may also be used in the case of conductive polymers. The thickness may be controlled by the amount of semiconductor initially deposited, or by removing deposited semiconductor by etching, such as chemical etching. The semiconductor layer may also be formed by applying a dispersion of fine particles of the semiconductor dispersed into a fluid, for example particles have an average diameter of 5 to 100 nm, including 10, 20, 30, 40, 50, 60, 70, 80 or 90 nm, dispersed in water, or an organic solvent for example alcohols such as methanol or ethanol, or mixtures thereof. Sintering may be desirable to remove the solvent and/or improve the contact between the semiconductor layer and the first conductive layer, or to improve the crystallinity of the semiconductor layer. It is important that the semiconductor layer both conformal and compact. Ideally, the contact between the first conductive layer and the semiconductor layer should be an ohmic contact.

Atomic layer deposition may be carried out by chemical reaction of two compounds which react to form the semiconductor layer. The structure onto which the semiconductor layer is to be deposited is exposed to vapors of the first of the two chemicals, and then exposed to the vapors or gasses of the second of the two chemicals. If necessary, the exposure and/or reaction may be carried out at elevated temperatures. In some instances, byproducts of the reaction may need to be removed before repeating the process, by washing, evacuation, or by the passage of an inert gas over the structure. The process may be repeated until the desired thickness of the semiconductor layer is formed. For example, in the case of the transparent oxide semiconductors, which are typically compounds of a metal and oxygen, the first chemical may be a halide, such as a chloride, bromide or iodide, an oxychloride, oxybromide or oxyiodide, organometallic compounds, alkoxides of the metal and other ceramic precursor compounds (such as titanium isopropoxide), as well as mixtures thereof. The second chemical may be water (H₂O), oxygen (O₂ and/or O₃) or a gaseous oxidizing agent, for example N₂O, as well as mixtures thereof. Inert gasses, such as helium, argon or nitrogen may be used to dilute the gasses during the process.

In a preferred alternative embodiment, the semiconductor layer is composed of TiO₂ nanowires. The nanowires may be prepared by solvothermal method with controllable length-to-diameter ratio and are well separated.⁷⁸ Preferably, the length of the TiO₂ nanowires is 400-1100 nm, more preferably 600-1000 nm, including 700, 800 and 900 nm.

The light-harvesting material is preferably a perovskite absorber. A “perovskite absorber” is a compound of formula ABX₃, where A is a metal atom such as lead or tin, B is a counter ion (typically an alkyl ammonium compound), and X is a halide (F, Cl, Br, or I) or pseudohalide (such as SCN), which forms crystals of the perovskite structure. Examples include CH₃NH₃PbX₃ (3-dimensional perovskite) and H₂NCHNH₂PbX₃ (3-dimensional perovskite) and CH₃NH₃Pb(SCN)₂I (Ruddlesden-Popper type). Examples of structure which are perovskite structures included 3-dimensional perovskite, Ruddlesden-Popper type and Dion-Jacobson type. In some cases, the perovskite absorber is doped, which may result in additional atoms located in interstitial sites and/or the formation of vacancies. Examples of a perovskite absorber that is doped included CH₃NH₃PbI3:10% PbSe, which is CH₃NH₃PbI₃ doped with 10% PbSe, and therefore the stoichiometry may deviate from the ABX₃ formula.

Preferably, the light-harvesting material is applied by spin-coating so that it fills spaces on and in the semiconductor layer. Preferably, the perovskite absorber is doped with PbSe. Preferably the perovskite material is doped with 5 to 20% PbSe, most preferably with 9-11% PbSe.

The hole-transporting material may be a solid p-type semiconductor, for example CuI, CuSCN, CuAlO₂, NiO, and mixtures thereof, as well as p-doped conductive polymers. Conductive polymers include poly(acetylene)s, poly(pyrrole)s, poly(thiophene)s, polyanilines, polythiophenes, poly(p-phenylene sulfide), poly(para-phenylene vinylene)s (PPV) and PPV derivatives, poly(3-alkylthiophenes), polyindole, polypyrene, polycarbazole, polyazulene, polyazepine, poly(fluorene)s, and polynaphthalene. Other examples include polyaniline, polyaniline derivatives, polythiophene, polythiophene derivatives, polypyrrole, polypyrrole derivatives, polythianaphthene, polythianaphthane derivatives, polyparaphenylene, polyparaphenylene derivatives, polyacetylene, polyacetylene derivatives, polydiacethylene, polydiacetylene derivatives, polyparaphenylenevinylene, polyparaphenylenevinylene derivatives, polynaphthalene, and polynaphthalene derivatives, polyisothianaphthene (PITN), polyheteroarylenvinylene (ParV), in which the heteroarylene group can be for example thiophene, furan or pyrrol, polyphenylene-sulphide (PPS), polyperinaphthalene (PPN), and polyphthalocyanine (PPhc), and their derivatives, copolymers thereof and mixtures thereof. As used herein, the term derivatives means the polymer is made from monomers substituted with side chains or groups. P-doping of the solid semiconductor and the conductive polymers may be carried out chemically, if necessary, for example by treatment with an oxidizing agent, such as oxygen, fluorine or iodine, or by electrochemical oxidation. A preferred hole-transporting material is spiro-MeOTAD (2,2′7,7′-tetrakis(N,N-di-p-methoxyphenyl amine)-9,9′-spirobifluorene).

A second conductive layer is in contact with the hole-transporting material, and is preferably formed of a highly conductive and chemically unreactive material, for example gold, platinum, or metallic alloys. Preferably, the second conductive layer is nickel or a nickel alloy. The second conductive layer may be present on a third conductive layer, which may be formed of any conductive material. The second conductive layer serve to transport electrons back to the hole-transporting material, thus completing the electrical circuit. The second conductive layer is preferably on a support, which may be formed of any solid material, such as plastic, glass or metal. Preferably, the second conductive layer is formed by evaporation or sputtering.

EXAMPLES

Chemicals and Materials Synthesis

Methylamine solution (CH₃NH₂, 40 wt. % in H₂O) and γ-Butyrolactone (GBL, ≥99%) were purchased from Aldrich. Hydriodic acid (HI, 57% w/w aq. soln.), lead(II) iodide (PbI₂, 99.9985% metals basis) and N,N-Dimethylformamide (DMF, anhydrous) were purchased from Alfa Aesar. Ethyl ether (anhydrous), and hydrochloric acid (HCl, 37.0%) were purchased from Fisher Chemical. Lead acetate (Pb(C₂H₃O₂)₂.3H₂O) was purchased from Mallinckrodt and sodium sulfide Na₂S.9H₂O was purchased from Aldrich. All chemicals were used without further purification.

Perovskite films were prepared through a combination of PbI, methylammonium iodide and PbSe or PbS. PbI was purchased through Alfa Aesar without additional processing. Methylammonium lead iodide was synthesized using a 1:1.5 molar ratio of HI (Sigma) and methylamine (Sigma Aldrich). This was mixed, and washed with ether to produce a white crystalline solid. PbSe was synthesized using lead acetate (Alfa Aesar) and selenium oxide. Selenium oxide was dissolved in water and adjusted to a pH of 1. Lead acetate was then added and a white precipitate formed, which was washed thoroughly with deionized water. PbS was synthesized through the addition of Na₂S (Sigma Aldrich) to lead acetate in aqueous environment in a 1:1 molar ratio. The resulting black precipitate was washed 5 times with deionized water and allowed to dry at 100° C. Solutions were made using a 9:1 ratio of PbI₂:PbS without out changing the concentration of methyl ammonium iodide. Care was taken to reduce oxidation of PbS and PbSe powders after preparation.

CH₃NH₃I was synthesized according to methods reported in literature¹² with slight modifications. In detail, HI was slowly introduced to equimolar CH₃NH₂ in a 200 mL round bottom flask immersed in an ice bath, with the solution being stirred continuously. The solution was allowed to react for 2 hours under stirring, then rotary evaporated at 60° C. until all solvent was removed. As obtained yellow solid was washed with ethyl ether six times, followed by vacuum filtration. Finally, the solid was dried at 120° C. in an oven overnight to give pure CH₃NH₃I product, exhibiting a white color. PbSe was synthesized by first adjusting an aqueous solution of SeO₂ to a pH of 2 using HCl, which was then mixed with Pb(C₂H₃O₂)₂.3H₂O in a 1:1 molar ratio. The solution was stirred for 12 hours at 80° C. The resulting white-pink solid was washed 5 times with excess deionized water and dried in an oven at 120° C. overnight.⁴⁶ The obtained powder was characterized using EDX measurements to confirm the purity of PbSe. Similarly, PbS was synthesized by adding equimolar amounts of Pb(C₂H₃O₂)₂.3H₂O and Na₂S.9H₂O to deionized water and allowing to stir for a 1 hour. The resulting black precipitate was washed thoroughly with deionized water and characterized with EDX to confirm purity.

Solution Synthesis

In the case of 10 w/w % of PbSe doping, it is defined as 10 w/w % of PbSe in the initial total mass of PbSe and PbI₂. Explicitly, 0.04 g of PbSe was dissolved in 0.7 ml of γ-butyrolactone with 0.360 g PbI₂ and 0.149 g CH₃NH₃I, resulting in a 9:1 weight ratio of PbI₂ to PbSe. The resulting mixture was stirred at 80° C. for 15 hours to yield a dark red solution. The doping level of PbS is similarly defined.

Accelerated Moisture Stability Experiment Setup

The accelerated moisture stability tests were carried out in a modified, glass-enclosed two-chamber system. The internal glass chamber was suspended in 40° C. deionized water inside of a larger glass vessel and held the tested samples, keeping the samples from direct contact with the liquid water. The external chamber was filled partially with deionized water, covered and heated to 40° C. The chamber was exposed to ambient light. This set up allowed the samples in the internal chamber to be exposed to water vapor generated in the surrounding water bath without direct contact to the water. The humidity was tested using a portable humidity tester and confirmed at 100% once the temperature reached 40° C.

Both pristine CH₃NH₃PbI₃ and PbSe-doped CH₃NH₃PbI₃ films were deposited on TiO₂-coated FTO glass substrates by spin coating at speed of 2000 rpm, followed by annealing at 120° C. for 60 minutes. It was previously demonstrated that single-step spin-coating of pure CH₃NH₃PbI₃ precursor solution results in thin films with low surface coverages, non-uniform thicknesses and varying crystal structures riddled with pin holes,^(4,15,47,48) which subsequently plagues charge transport in solar cells by means of short circuiting the material and causing decreased range electron transfers. Surprisingly, single-step deposition of PbSe-doped CH₃NH₃PbI₃ precursor solution leads to films with high surface coverage and large-size grains, without the need for anti-solvent use, as shown in FIG. 2A. However, cracks between large grains are observed, which may be due to the inherent nature of perovskites, as the films form from nucleation points, creating large “grains” and inherent grain boundaries. In order to confirm the existence of Se in 10% w/w PbSe doped sample, we set out to perform energy-dispersive X-ray analysis (EDX) on the fabricated thin film. FIG. 2B shows the EDX spectrum of spin-coated 10% w/w PbSe doped CH₃NH₃PbI₃ thin film. Clearly, the spectrum confirms the findings of Se, through the peaks at around 1.4 keV, 11.2 keV and 12.5 keV energies. Additionally, the spectrum also indicates the persistence of Pb and I, which are the main components of inorganic framework of perovskite CH₃NH₃PbI₃. Characteristically, Pb was identified through peaks at around 1.8 keV, 2.4 keV, 10.6 keV and 12.6 keV. The high intensities of Pb and I signals as illustrated in the spectrum account for the natures of Pb and I being electron-rich atoms that have strong interactions with X-rays. Qualitatively, Table 1, below, summarizes the elemental analysis by EDX confirming the desired amount of PbSe present in the prepared film compared to theoretically calculated percentages. Nitrogen was removed from the calculations due to overlapping carbon and nitrogen peaks, artificially increasing the percentage of both carbon and nitrogen. This further allowed for a more accurate percentage of low concentration atoms to be calculated. In Table 1 the average was taken based on the three separate measurements. Each measurement was taken at a different point on the thin film surface.

TABLE 1 Summary of EDX measurements for 10% w/w PbSe doped CH₃NH₃PbI₃. Av. Theoretical Element Weight % Weight % Weight % Weight % for 10 w % C 5.29 5.42 5.40 5.37 2.1% Se 1.03 .93 .81 .92 1.3% I 59.59 60.16 62.30 60.69 61.83%  Pb 34.10 33.50 31.49 33.03 34.8% 

The evaluations of the moisture stabilities of pristine CH₃NH₃PbI₃ and 10% w/w PbSe-doped CH₃NH₃PbI₃ films were conducted by time-dependent reflectance measurements, at an accelerated manner, with the details of accelerated moisture-exposure experiment setup given in Experimental Details section. The reflectance spectra of both films show the change of optical reflectance spectra as a function of exposure time in 100% humidity under ambient illumination. FIG. 2C shows the evolution of reflectance of pristine CH₃NH₃PbI₃ thin film, with inset pictures being the photographs of tested film at 0 minute (left) and 30 minutes (right) of aging time. At initial time of moisture exposure (black plot), CH₃NH₃PbI₃ film displays a reflectance profile where the percentage of light reflected is low (<˜16%) between 600 and 775 nm. Reflectance then elevates drastically between 775 nm and 825 nm which notes the onset of material reflectance. Even only after 30 minutes of moisture exposure (red plot), the aged CH₃NH₃PbI₃ film already shows an apparent blue shift of reflectance onset, along with the total upshift in amount of light reflected. The CH₃NH₃PbI₃ experienced significant degradation after aging in ˜100% moisture environment for only 30 minutes based on our test conditions. In phenomenal contrast, FIG. 2D shows the evolution of reflectance of 10% w/w PbSe doped CH₃NH₃PbI₃ film, with insets also being photographs of tested films at corresponding aging times (0 hour, left; 60 hours, right). FIG. 11A shows a photograph of tested CH₃NH₃PbI₃ film at 0 minutes of aging time. FIG. 11B shows a photograph of tested CH₃NH₃PbI₃ film at 30 minutes of aging time. The closely overlapped time-dependent spectra from 0 hours up to even 96 hours of 10% w/w PbSe doped CH₃NH₃PbI₃ film, demonstrates enhanced moisture stability. Defining “stability” as the stability of the reflectance spectra over exposure time in 100% humidity under ambient illumination, the 10% w/w PbSe doped CH₃NH₃PbI₃ film exhibits over two-hundred-fold stability compared to the pure CH₃NH₃PbI₃. FIG. 2D shows that the final degradation of 10% w/w PbSe-doped CH₃NH₃PbI₃ occurred after 120 hours, as shown by the increase in reflectance at 800 nm from 15% to 20%. FIG. 12A shows a photograph of tested 10% w/w PbSe doped CH3NH3PbI3 film at 0 minutes of aging time. FIG. 12B shows a photograph of tested 10% w/w PbSe doped CH₃NH₃PbI₃ film at 60 minutes of aging time. To validate the trend of doping effects on the evolution of reflectance spectra, we also performed reflectance tests on 5% w/w PbSe-doped CH₃NH₃PbI₃ films, as shown in FIG. 4. Results confirm that as the doping percentage decreased, so did the chemical stability of the film. Utilizing half of the dopant concentration, the stability of the resultant film exhibited a little more than half of the stability of the 10% w/w film, lasting a remarkable 65 hours in humid air. This confirms that the stability is dependent on the concentration of dopant used and follows a steady trend relative to concentration.

FIG. 2F presents the band gap for 10% w/w PbSe-doped CH₃NH₃PbI₃, which exhibited an increase after 48 hours from 1.527 eV to 1.532 eV, most likely due to the formation of a stable hydrated crystal, finally degrading at 1.535 eV. Likewise, FIG. 2E shows the corresponding bandgap for pristine CH₃NH₃PbI₃, with corresponding band gap of 1.535 eV and a degraded bandgap at 1.475 eV. Obviously, the band gap of PbSe-doped CH₃NH₃PbI₃ changed little and was shown to be comparable with that of reported pure CH₃NH₃PbI₃ perovskite film, which exhibits a band gap of 1.53-1.54 eV. This remarkably enhanced stability in moisture can be attributed to the structural integrity through electrostatic interaction between Se²⁻ and the adjacent positively charged methylammonium cations. The electrostatic interaction reduces the detrimental effect of atmospheric water by washing out the cationic organic moieties. Previous studies have shown evidence of hydrogen-bonding-like electrostatic interaction between inorganic framework and methylammonium cations.⁴⁹⁻⁵¹ If water does penetrate the lattice, the increased covalent nature of the PbSe bonding stabilizes the lattice, and allows for retained rigidity and durability of the crystal lattice. From a fundamental material synthesis view, increasing electrostatic interactions at a balanced level will further allow chemical stability and integrity in perovskite materials.

As presented in previous studies, increasing the cubic nature (P4 mm, Pm3m) of perovskite (peaks at 2θ=14°, 23°, 29°, 32°, 41°) and reducing the orthogonal/tetragonal nature (Pnma, I4/mcm respectively) (peaks at 2θ=28°, 31°, 44°) in hybrid organic-inorganic perovskites imparts an inherent chemical stability to the material.^(51,52) This phenomenon has been observed with the introduction of formamidinium and inorganic dopants.^(53,54) FIG. 2G reinforces this observation, showing that all of the inherently cubic peaks increase while the orthogonal/tetragonal peaks show an inherent decrease in relative intensity when doped with PbSe. There are no peaks for PbSe, supporting the idea that the Se⁻ ions are incorporated into the lattice structure, rather than as a separated phase. From a fundamental level, the Jahn-Teller effect predicts that as the covalent nature increases and the size of dopant atoms decreases, the lattice will shift to a more cubic nature with higher linearity in the bond structure. The identifiable peaks exhibit a fundamental property of hybrid organic-inorganic perovskites, that is, by changing the nature and crystalline phase of the perovskite from a tetragonal dominant phase to a cubic dominant phase, a higher overall water resistance can be achieved.

In order to verify the proposed electrostatic attraction between incorporated Se²⁻ and cationic CH₃NH₃ ⁺, pristine CH₃NH₃PbI₃ and 10% w/w PbSe doped CH₃NH₃PbI₃ thin films were further characterized on infrared spectroscopy to illustrate N—H vibrations, by means of frequency changes associated with the affected N—H vibrations. FIG. 2H shows the infrared spectra of CH₃NH₃PbI₃ (darker) and 10% w/w PbSe doped CH₃NH₃PbI₃ (lighter) thin films, with peak at around 3201 cm⁻¹ of CH₃NH₃PbI₃ corresponds to N—H stretch.^(40,58,59) N—H stretching modes at 3201 cm⁻¹ in CH₃NH₃PbI₃ films is redshifted to about 3114 cm⁻¹ in 10% w/w PbSe doped films due to the electrostatic attraction effects between the Se²⁻ and cationic CH₃NH₃ ⁺. This demonstrates that electronegative particles retard stretching modes of atoms when it comes to linearly aligned interactions, such as hydrogen bonding.⁶⁰ Also, significant band broadening is witnessed on N—H stretch in 10% w/w PbSe doped CH₃NH₃PbI₃, relative to the peak of N—H stretch in pristine CH₃NH₃PbI₃. This band broadening suggests the existence of strong electrostatic interaction in material systems.⁶¹ Apart from the redshift of stretching frequency, no obvious change of N—H bending frequency was observed between CH₃NH₃PbI₃ and doped CH₃NH₃PbI₃ thin-film samples. This is likely due to the two-dimensional bending modes along with the relatively scarce Se²⁻ (˜18 mol %) in the doped system, that cannot enable a spatially favored electronic wave function overlap between partially cationic ammonium hydrogen atoms and anionic Se²⁻. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to verify the intercalation of Se²⁻ into the crystal lattice of CH₃NH₃PbI₃, rather than as a separate phase.

To further solidify the fundamental interactions of chalcogenide doping in organic-inorganic perovskites, bivalent sulfide in the form of PbS, was also tested as an alternative chalcogenide dopant, with S having a greater electronegativity than Se. As shown in FIG. 6A and FIG. 6B, PbS-doped CH₃NH₃PbI₃ exhibits an even greater improved stability in humid environments. However, due to its higher ionic nature, and small ionic radius, a lower photovoltaic performance of PbS-doped CH₃NH₃PbI₃-based solar cells was observed as shown by the J-V curve in FIG. 8. Although PbS may not be a suitable dopant in this regard, the PbS-doped CH₃NH₃PbI₃ film, the results provide support for the fundamental interactions occurring through chalcogenide doping, in regard to stability to moisture. The same trend as PbSe-doped CH₃NH₃PbI₃ can be seen in the XRD pattern of PbS doped CH₃NH₃PbI₃ (FIG. 7), and this result strengthens the claims that as cubic nature increases, as observed with XRD, tetragonal/orthorhombic nature decreases, and chemical stability of the perovskite material increases. Thus, we show that electronegativity effect is supported by both PbSe and PbS doping.

Photocurrent density-voltage (J-V) measurements were conducted to examine the photovoltaic performance of the 10% w/w PbSe doped CH₃NH₃PbI₃ device. The J-V curves of 10% w/w PbSe doped CH₃NH₃PbI₃ champion cell are illustrated in FIG. 3A. Power conversion efficiency (PCE) achieved on the champion cell through reverse scan was 10.4% and corresponding short-circuit current density, open-circuit voltage and fill factor were 16.73 mA/cm², 0.942 V and 0.662, respectively; whereas forward scan (low voltage to high voltage scan) led to an 8.6% conversion efficiency with corresponding short-circuit current density, open-circuit voltage and fill factors of 16.82 mA/cm², 0.911 V and 0.561, respectively; note that the difference of photovoltaic characteristics between two scan directions indicated a hysteresis during cell operation. As shown in FIG. 3B, stabilized output of 9.93% PCE and 13.81 mA/cm² current density was achieved, which echoes the photovoltaic parameters obtained from J-V scans, and validates the phenomenal solar cell performance realized on the 10% w/w PbSe-doped CH₃NH₃PbI₃ device. The data demonstrates that a chemical dopant with an electronic order higher than monovalent pseudohalides^(4,30,55), can retain substantial photovoltaic properties in addition to the significantly enhanced chemical stabilities.

Ideally, the doping approach should not excessively tamper with the perovskite structures of studied samples, for preserving the desired charge transport properties. To probe the optoelectronic profiles-photocarrier generation and collection processes happening in the PbSe doped CH₃NH₃PbI₃, the incident photon-to-current efficiency (IPCE) on the 10% w/w PbSe doped CH₃NH₃PbI₃ thin film was measured, as shown in FIG. 3C. The IPCE spectrum displays a high external quantum efficiencies that are ˜60% in average between 375 nm and 750 nm, accounting for substantial charge generation and collection in the visible light region. When wavelength of incident photons exceeds 750 nm, external quantum efficiency starts to drastically decay, approaching zero starting from 800 nm, which corresponds to a ˜1.5 eV bandgap, as being similar to IPCE spectra of undoped CH₃NH₃PbI₃ reported previously.^(56,57) The comparable shapes of IPCE spectra of both doped and pristine CH₃NH₃PbI₃ films confirm the fact that perovskite photoelectric characteristics are largely unaffected with the presence of 10% w/w PbSe dopant in the structure.

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What is claimed is:
 1. A light-harvesting material, comprising: a perovskite absorber doped with a metal chalcogenide, wherein the perovskite absorber has the formula ABX₃, A is selected from the group consisting of methyl ammonium, formamidinium and mixtures thereof, B is lead, X is I, and the metal of the metal chalcogenide is lead, the chalcogenide of the metal chalcogenide is selected from the group consisting of S, Se and mixtures thereof, and the metal chalcogenide is present in an amount of 5 to 10 percent by weight.
 2. The light-harvesting material of claim 1, wherein A is methyl ammonium, and the chalcogenide of the metal chalcogenide is Se.
 3. A photovoltaic device, comprising: (1) a first conductive layer, (2) optionally an electron blocking layer, on the first conductive layer, (3) a semiconductor layer, on the first conductive layer, (4) a light-harvesting material, on the semiconductor layer, (5) a hole transport material, on the light-harvesting material, and (6) a second conductive layer, on the hole transport material, wherein the light-harvesting material comprises a perovskite absorber doped with a metal chalcogenide, the perovskite absorber has the formula ABX₃, A is selected from the group consisting of methyl ammonium, formamidinium and mixtures thereof, B is lead, X is I, and the metal of the metal chalcogenide is lead, the chalcogenide of the metal chalcogenide is selected from the group consisting of S, Se and mixtures thereof, and the metal chalcogenide is present in an amount of 5 to 10 percent by weight.
 4. The photovoltaic device of claim 3, wherein A is methyl ammonium, and the chalcogenide of the metal chalcogenide is Se.
 5. The photovoltaic device of claim of claim 3, further comprising the electron blocking layer.
 6. The photovoltaic device of claim 3, wherein the first conductive layer is transparent.
 7. The photovoltaic device of claim 6, wherein the first conductive layer comprises at least one transparent conductor selected from the group consisting of indium-tin oxide, fluorinated tin oxide and aluminum-zinc oxide.
 8. A method of making the light-harvesting material of claim 1, comprising: forming a solution comprising: a first component selected from the group consisting of methyl ammonium, formamidinium and mixtures thereof, a second component of lead, a third component of I, and a fourth component selected from the group consisting of S, Se, and mixtures thereof, and forming the light-harvesting material from the solution.
 9. The method of claim 8, further comprising depositing the light-harvesting material on a semiconductor layer by spin-coating.
 10. A method of forming the photovoltaic device of claim 3, comprising: forming the first conductive layer, and optionally the blocking layer on the first conductive layer; forming the semiconductor layer, on the first conductive layer; applying the light-harvesting material, onto the semiconductor layer; forming the hole transport layer, on the semiconductor layer; and forming the second conductive layer, on the hole transport layer.
 11. The method of claim 10, wherein forming the semiconductor layer comprises a solvothermal method.
 12. The method of claim 10, wherein forming the second conductive layer comprises sputtering or evaporation.
 13. The method of claim 10, wherein applying the light-harvesting material comprises spin coating. 